EP4190853A1 - Foam molding composition, foamed molded body, electric wire, method for manufacturing foamed molded body, and method for manufacturing electric wire - Google Patents

Foam molding composition, foamed molded body, electric wire, method for manufacturing foamed molded body, and method for manufacturing electric wire Download PDF

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Publication number
EP4190853A1
EP4190853A1 EP21852439.5A EP21852439A EP4190853A1 EP 4190853 A1 EP4190853 A1 EP 4190853A1 EP 21852439 A EP21852439 A EP 21852439A EP 4190853 A1 EP4190853 A1 EP 4190853A1
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EP
European Patent Office
Prior art keywords
foam molding
molding composition
resin
electric wire
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21852439.5A
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German (de)
English (en)
French (fr)
Other versions
EP4190853A4 (en
Inventor
Hideki KOUNO
Kenji Ishii
Masato TOKUDA
Takahiro Kitahara
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Daikin Industries Ltd
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Daikin Industries Ltd
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Publication date
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Publication of EP4190853A1 publication Critical patent/EP4190853A1/en
Publication of EP4190853A4 publication Critical patent/EP4190853A4/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/046—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0038—Use of organic additives containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C09D181/04—Polysulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/307—Other macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2207/00—Foams characterised by their intended use
    • C08J2207/06—Electrical wire insulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2481/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters

Definitions

  • the present disclosure relates to a foam molding composition, a foam molded body, an electric wire, a method for producing a foam molded body and a method for producing an electric wire.
  • the foams using a resin as their materials are obtained usually by foam molding in which the resin melted is molded in the state that gas is made to be present in the resin.
  • cells in the foam are fine and homogeneously distributed, in order to make the shape and characteristics of the foam obtained to be uniform.
  • a foam nucleating agent to be present in the resin so as to make a starting point to generate the cells during foam molding.
  • Patent Literature 1 discloses a foam nucleating agent which contains at least one compound selected from the group consisting of phosphate complex compounds (a-1) and phosphorus-based ester compounds (a-2), and has an average particle size of 0.01 ⁇ m to 300 ⁇ m, and a composition for a foam, which contains the foam nucleating agent and a resin component (B) being at least one component selected from the group consisting of elastomers (b-1) and thermoplastic resins (b-2).
  • a foam nucleating agent which contains at least one compound selected from the group consisting of phosphate complex compounds (a-1) and phosphorus-based ester compounds (a-2), and has an average particle size of 0.01 ⁇ m to 300 ⁇ m
  • a composition for a foam which contains the foam nucleating agent and a resin component (B) being at least one component selected from the group consisting of elastomers (b-1) and thermoplastic resins (b-2).
  • Patent Literature 2 discloses an insulated electric wire which has a conductor and a foamed insulator formed on the circumference of the conductor and having a foamed region, wherein the foamed insulator is composed of a resin composition containing a polyphenylene sulfide resin and alumina, and the foaming degree of the foamed insulator is 30% or higher and 80% or lower.
  • Patent Literature 3 discloses a foamed electric wire which has a conductor and a foamed insulating layer, wherein the foamed insulating layer is composed of a thermoplastic resin in which the melting point of a crystalline thermoplastic resin or the glass transition point of a noncrystalline thermoplastic resin is 150°C or higher, and has an average cell size of 5 ⁇ m or smaller.
  • Patent Literature 4 discloses a composition for a wallpaper which is made by adding a foaming agent and an aromatic cyclic phosphoric acid ester salt having a specific structure as a foam nucleating agent to a thermoplastic elastomer.
  • An object of the present disclosure is to provide a foam molding composition from which there can be produced a foam molded body and a foamed electric wire which are excellent in the heat resistance, small in the average cell size, high in the foaming ratio, and little in generation of sparks.
  • the present disclosure relates to a foam molding composition which comprises a resin (A) having a pyrolysis temperature of 330°C or higher and at least one compound (B) selected from the group consisting of phosphoric acid esters and salts thereof and phosphoric acid ester complex compounds.
  • the resin (A) has a dielectric constant of 4.0 or lower.
  • the resin (A) is capable of being melt processed.
  • the resin (A) has a melting point of 250°C or higher.
  • the resin (A) is at least one selected from the group consisting of polyphenylene sulfide (PPS) and polyaryl ether ketone (PAEK).
  • the compound (B) has a melting point of 300°C or higher.
  • the compound (B) is an aromatic cyclic phosphoric acid ester salt represented by the following formula (1).
  • R 1 , R 2 , R 3 and R 4 each represent a hydrogen atom, an alkyl group or cycloalkyl group having 1 to 8 carbon atoms, or an aryl group, alkylaryl group or arylalkyl group having 6 to 12 carbon atoms;
  • R 5 and R 6 each represent a hydrogen atom or a methyl group;
  • n represents an integer of 1 or 2;
  • m represents an integer of 0 to 2; and
  • X represents a m+n-valent metal.
  • R 1 and R 2 in the above formula (1) are a t-butyl group.
  • X in the above formula (1) is sodium.
  • the above compound (B) is 2,2'-methylenebis(4,6-di-t-butylphenyl) sodium phosphate.
  • the present disclosure is also a foam molded body characterized in being obtained from the above-mentioned foam molding composition.
  • the foam molded body has a foaming ratio of 10% or higher.
  • the present disclosure is also an electric wire characterized in comprising a core wire and a covering material covering the core wire and obtained from the above-mentioned foam molding composition.
  • the covering material of the electric wire has a foaming ratio of 10% or higher.
  • the present disclosure is also a method for producing a foam molded body, characterized in comprising foam molding the above-mentioned foam molding composition.
  • the present disclosure is also a method for producing an electric wire, characterized in comprising covering a core wire with the above-mentioned foam molding composition to obtain the electric wire.
  • the foam molding composition of the present disclosure having the above constitution enables to produce a foam molded body and a foamed electric wire which are high in the foaming ratio, small in the average cell size, little in generation of sparks, low in variations in the outer diameter and the electrostatic capacity and smooth in the surface.
  • the compound (B) has a melting point of 300°C or higher, the performance effect becomes remarkable.
  • the molding temperature of the above-mentioned functional plastic is high, when a general-purpose foam nucleating agent is blended, the foam nucleating agent ends in melting during molding and poses difficulty with the effective action.
  • the compound (B) one having a melting point of 300°C or higher is used, such a problem is more suitably solved.
  • the resin (A) in the present disclosure has a pyrolysis temperature of 330°C or higher. Since the resin (A) has a high pyrolysis temperature as described above, the foam molding composition of the present disclosure can have high heat resistance and excellent mechanical characteristics.
  • the pyrolysis temperature is preferably 350°C or higher and more preferably 400°C or higher.
  • the pyrolysis temperature is a 1%-weight loss temperature when heated in air at 10°C/min in TG (heat weight change measurement).
  • the dielectric constant of the resin (A) is 4.0 or lower, in order to make low the signal loss of a communication electric wire.
  • the dielectric constant is more preferably 3.8 or lower and still more preferably 3.5 or lower.
  • the dielectric constant is measured by a cavity resonator method at a frequency of 6 GHz.
  • the melting point of the resin (A) is 200°C or higher or the molding temperature thereof is 250°C or higher, since there can be obtained a foam molded body excellent in heat resistance and having a wide continuous use temperature range from the resin (A). Further, it is more preferable that the melting point is 250°C or higher or the molding temperature is 300°C or higher.
  • the melting point is a temperature measured by a differential scanning calorimeter (DSC);
  • the molding temperature is a usually recommended temperature suitable for molding, and the temperature at which the resin (A) has flowability and no resin deterioration such as coloring occurs; and "having flowability" means that the MFR at the temperature is 0.0001 or higher.
  • the melt flow rate (MFR) of the resin (A) as measured under the condition of 380°C and a load of 5,000 g is preferably 1 to 150 g/10 min, more preferably 5 to 130
  • the resin (A) is preferably a melt processable one.
  • the resin (A) specifically includes polyaryl ether ketones (PAEK)(more specifically, for example, polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ketone (PEK) and polyether ether ketone ketone (PEEKK)), polyphenylene sulfide (PPS), polyether sulfone (PES), liquid crystal polymers (LCP), polysulfone (PSF), noncrystalline polyarylate (PAR), polyether nitrile (PEN), thermoplastic polyimide (TPI), polyimide (PI), polyether imide (PEI), polyamideimide (PAI) and fluororesins.
  • PAEK polyaryl ether ketones
  • the resin (A) is preferably at least one selected from the group consisting of liquid crystal polymers (LCP), polyphenylene sulfide (PPS), polyether sulfone (PES) and polyaryl ether ketone (PAEK), and especially preferably at least one selected from the group consisting of polyphenylene sulfide (PPS) and polyaryl ether ketone (PAEK).
  • LCP liquid crystal polymers
  • PPS polyphenylene sulfide
  • PES polyether sulfone
  • PAEK polyaryl ether ketone
  • the resin (A) can be used in one kind or in two or more kinds.
  • PAEK polyaryl ether ketone
  • Examples of the divalent aromatic hydrocarbon ring group represented by Ar include arylene groups having 6 to 10 carbon atoms, such as a phenylene group (o-, m- or p-phenylene group) and a naphthylene group, biarylene groups (each arylene group has 6 to 10 carbon atoms), such as a biphenylene group (2,2'-bipheylene group, 3,3'-biphenylene group, 4,4'-biphenylene group or the like), and terarylene groups (each arylene group has 6 to 10 carbon atoms), such as an o-, m- or p-terphenylene group.
  • arylene groups having 6 to 10 carbon atoms such as a phenylene group (o-, m- or p-phenylene group) and a naphthylene group
  • biarylene groups each arylene group has 6 to 10 carbon atoms
  • terarylene groups each arylene group has 6 to 10
  • aromatic hydrocarbon ring groups optionally have a substituent, for example, a halogen atom, an alkyl group (a linear or branched chain alkyl group having 1 to 4 carbon atoms, such as a methyl group), a haloalkyl group, a hydroxyl group, an alkoxy group (a linear or branched chain alkoxy group having 1 to 4 carbon atoms, such as a methoxy group), a mercapto group, an alkylthio group, a carboxyl group, a sulfo group, an amino group, an N-substituted amino group or a cyano group.
  • a substituent for example, a halogen atom, an alkyl group (a linear or branched chain alkyl group having 1 to 4 carbon atoms, such as a methyl group), a haloalkyl group, a hydroxyl group, an alkoxy group (a linear or branched chain alkoxy group having 1 to 4
  • each Ar may be identical to each other, or may be different from each other.
  • a preferable Ar is a phenylene group (for example, p-phenylene group), or a biphenylene group (for example, a 4,4'-biphenylene group).
  • resins having the repeating unit (a1) include polyether ketone (for example, "PEEK-HT", manufactured by Victrex pic).
  • resins having the repeating unit (a2) include polyether ketone ketone (for example, "PEKK”, manufactured by Arkema+Oxford Performance Material Co.).
  • resins having the repeating unit (a3) include polyether ether ketone (for example, “VICTREX PEEK”, manufactured by Victrex plc, “Vestakeep(R)”, manufactured by Evonik Degussa GmbH, “Vestakeep-J”, manufactured by Daicel-Evonik Ltd.), “KetaSpire(R)", manufactured by Solvay Specialty Polymers USA, LLC), and polyether-diphenyl-ether-phenyl-ketone-phenyl (for example, "Kadel(R)", manufactured by Solvay Specialty Polymers USA, LLC).
  • polyether ether ketone for example, "VICTREX PEEK", manufactured by Victrex plc, "Vestakeep(R)", manufactured by Evonik Degussa GmbH, “Vestakeep-J”, manufactured by Daicel-Evonik Ltd.
  • KetaSpire(R) manufactured by Solvay Specialty Polymers USA, LLC
  • resins having the repeating unit (a4) include polyether ketone ether ketone ketone (for example, "VITREX ST", manufactured by Victrex pic).
  • resins having the repeating unit (a5) include polyether ether ketone ketone.
  • ether segment imparts flexibility to a molecular chain and the ketone segment imparts rigidity to the molecular chain, the more the ether segment, the higher the crystallization rate and the higher the degree of crystallinity finally reachable; the more the ketone segment, the glass transition temperature and the melting point are likely to become higher.
  • aromatic polyether ketone resins can be used singly or in a combination of two or more.
  • an aromatic polyether ketone resin having any of the repeating units (a1) to (a4) is preferable. It is preferable that, for example, the aromatic polyether ketone resin is at least one resin selected from the group consisting of polyether ketone, polyether ether ketone, polyether ketone ketone and polyether ketone ether ketone ketone. It is more preferable that the aromatic polyether ketone resin is at least one resin selected from the group consisting of polyether ketone, polyether ether ketone and polyether ketone ketone. Polyether ketone ketone is especially preferable due to that the electric wire processability is improved and the dielectric constant is low.
  • the melting point of the aromatic polyether ketone resin is preferably 300°C or higher, and more preferably 320°C or higher. Due to that the melting point is in the above range, the heat resistance of a molded article to be obtained can be improved.
  • the glass transition temperature (Tg) of the aromatic polyether ketone resin is preferably 130°C or higher, and more preferably 135°C or higher and still more preferably 140°C or higher. Due to that the glass transition temperature is in the above range, an insulated electric wire excellent in the heat resistance can be obtained.
  • the upper limit of the glass transition temperature is not limited, but is, from the viewpoint of the moldability, preferably 220°C or lower and more preferably 180°C or lower.
  • the glass transition temperature is measured according to JIS K7121 by using a differential scanning calorimetry (DSC) device under the measurement condition of a temperature-increasing rate of 20°C/min.
  • DSC differential scanning calorimetry
  • the content of the resin (A) is, with respect to 100 parts by mass of the foam molding composition, preferably 50 parts by mass or higher, more preferably 80 parts by mass or higher, still more preferably 90 parts by mass or higher, further still more preferably 95 parts by mass or higher and especially preferably 98 parts by mass or higher.
  • the upper limit is 99.999 parts by mass or lower and more preferably 99.99 parts by mass or lower.
  • the compound (B) acting as a foam nucleating agent in the present disclosure is at least one compound selected from the group consisting of phosphoric acid esters and salts thereof, and phosphoric acid ester complex compounds.
  • the compound (B) is not melted at the molding temperature.
  • the melting point of the compound (B) is 300°C or higher. Being 350°C or higher is more preferable and being 400°C or higher is most preferable.
  • a phosphoric acid ester compound usable as the compound (B) is representatively a phosphoric acid ester, a phosphorous acid ester, an acidic phosphate ester, an acidic phosphite ester or a salt thereof with ammonia, an amine, melamine, an alkali metal, an alkaline earth metal or the like, and the specific structure thereof is not limited.
  • acidic phosphate esters or acidic phosphite esters such as triphenyl phosphate, trilauryl phosphate, tristearyl phosphate, trioleyl phosphate, xylene diphenyl phosphate, ethyl diphenyl phosphate, isopropyl diphenyl phosphate, n-butyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, cetyl diphenyl phosphate, stearyl diphenyl phosphate, oleyl diphenyl phosphate, butyl dicresyl phosphate, octyl dicresyl phosphate, lauryl dicresyl phosphate, dibutyl pyrophosphate, monophenyl acid phosphate, diphenyl acid phosphate, monocresyl acid phosphate, dic
  • More specific examples thereof include salts of phosphoric acid esters, such as bis(4-t-butylphenyl) sodium phosphate and 2,2-methylenebis(4,6-di-t-butylphenyl) sodium phosphate, and a sodium salt of (2-hydroxy-2-oxo-4,6,10,12-tetra-t-butyl-1,3,2-dibenzo[d,g]perhydrodioxaphosphocin.
  • the ester may be a mono-ester, a di-ester, a tri-ester or a more polyester. These may be used singly in one kind or in a combination of two or more kinds.
  • aromatic phosphoric acid esters are preferable; salts of aromatic phosphoric acid esters are more preferable; and salts of aromatic phosphoric acid esters having a cyclic structure are still more preferable.
  • aromatic cyclic phosphoric acid salts represented by the following formula (1) are especially preferable.
  • R 1 , R 2 , R 3 and R 4 each represent a hydrogen atom, an alkyl group or cycloalkyl group having 1 to 8 carbon atoms, or an aryl group, alkylaryl group or arylalkyl group having 6 to 12 carbon atoms;
  • R 5 and R 6 each represent a hydrogen atom or a methyl group;
  • n represents an integer of 1 or 2;
  • m represents an integer of 0 to 2; and
  • X represents a m+n-valent metal.
  • Examples of the alkyl groups represented by R 1 and R 2 in the above formula (1) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, sec-amyl, tert-amyl, hexyl, isohexyl, heptyl, octyl, isooctyl, 2-ethylhexyl and tert-octyl.
  • the cycloalkyl groups include cyclopentyl, cyclohexyl and cycloheptyl.
  • the aryl groups represented by R 1 and R 2 include phenyl, naphthyl and biphenyl.
  • the alkylaryl groups include 4-methylphenyl, 4-tert-butylphenyl and nonylphenyl.
  • the arylalkyl groups include benzyl, phenethyl and cumyl.
  • the metal represented by X includes alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, and aluminum, zinc and titanium.
  • R 1 and R 2 are each an alkylaryl group, and being a t-butylphenyl group is more preferable.
  • the metal represented by X is sodium, potassium, rubidium, calcium or barium, and among these, sodium is more preferable. More specifically, it is most preferable that the compound (B) is 2,2'-methylenebis(4,6-di-t-butylphenyl) sodium phosphate represented by the following formula (2). [Formula 3]
  • the phosphoric acid ester complex compound usable as the compound (B) is a complex composed of a metal and an organic compound having a phosphoric acid ester, and a specific structure thereof is not limited.
  • the organic compound constituting the complex compound include bis(4,4',6,6'-tetra-t-butyl-2,2'-methylene-diphenyl phosphate, 2,2'-methylene-bis(4,6-di-t-butylphenyl) phosphate, 2,2'-methylene-bis(4,6-dimethylphenyl) phosphate, 2,2'-methylene-bis(4,6-dimethylphenyl) phosphate, 2,2'-methylene-bis(4,6-diethylphenyl) phosphate, 2,2'-methylene-bis(4-methyl-6-t-butylphenyl) phosphate, 2,2'-methylene-bis(4-ethyl-6-t-butylphenyl) phosphate, 2,2'
  • examples of the metal constituting the phosphoric acid ester complex compound include aluminum, sodium, lithium, calcium, magnesium and barium. These may be used singly in one kind or in a combination of two or more kinds. Among these, aromatic phosphoric acid esters are preferable; cyclic aromatic phosphoric acid esters are still more preferable; and sodium complex compounds of aromatic cyclic phosphoric acid esters are most preferable.
  • examples of compounds having a melting point of 300°C or higher include 2,2'-methylenebis(4,6-di-t-butylphenyl) sodium phosphate.
  • the content of the compound (B) is, with respect to the total amount of the resin (A) and the compound (B), preferably 0.001 to 20 parts by mass.
  • the content of the compound (B) is too low, it becomes difficult for a covering material to be obtained to be provided with fine cells; and when too high, there arises such a risk that sparks are often generated during molding of an electric wire.
  • the foam molding composition of the present disclosure further contains boron nitride. Due to containing boron nitride, there is obtained a covering material having fine and uniform cells smaller in average cell size.
  • the average particle size of the boron nitride is preferably 8.0 ⁇ m or larger. Conventionally, the average particle size of boron nitride is likely to be made small and use of boron nitride having a relatively large average particle size has not been studied specifically.
  • the foam molding composition of the present disclosure contains boron nitride having an average particle size in the above specific range, there can be formed a foamed electric wire equipped with a covering material having a smaller average cell size and a high foaming ratio.
  • the average particle size of the boron nitride is more preferably 9.0 ⁇ m or larger, still more preferably 10.0 ⁇ m or larger, further still more preferably 10.5 ⁇ m or larger, especially preferably 11.0 ⁇ m or larger, especially more preferably 12.0 ⁇ m or larger and most preferably 13.0 ⁇ m or larger.
  • the average particle size of the boron nitride is preferably 25 ⁇ m or smaller and more preferably 20 ⁇ m or smaller.
  • the average particle size of the boron nitride is in the above range, a covering material having fine and uniform cells can be formed.
  • the average particle size of the boron nitride is a value determined by using a laser diffraction/scattering particle size distribution analyzer.
  • a medium may appropriately be selected, but for example, methanol or the like may be used.
  • the particle size distribution in terms of (D84-D16)/D50 of the boron nitride is preferably 1.2 or lower.
  • D84, D50 and D16 represent, respectively, a particle size ( ⁇ m) of a point of the cumulative curve which indicates 84%, a particle size ( ⁇ m) of a point thereof which indicates 50% and a particle size ( ⁇ m) of a point thereof which indicates 16%.
  • the cumulation of the particle size distribution is carried out from the small particle size side.
  • the total volume of the powder mass can be obtained by preparing a sample in which the powder of the boron nitride is dispersed in a medium such as methanol, and using a laser diffraction/scattering particle size distribution analyzer (for example, Microtrack MT3300, manufactured by Nikkiso Co., Ltd.).
  • a laser diffraction/scattering particle size distribution analyzer for example, Microtrack MT3300, manufactured by Nikkiso Co., Ltd.
  • the particle size distribution of the boron nitride is in the above range, a covering material having fine and uniform cells can be formed and generation of sparks can be suppressed more.
  • the particle size distribution is more preferably 1.1 or less and still more preferably 1.0 or lower.
  • the lower limit of the particle size distribution is not limited, but may be, for example, 0.1.
  • the cumulative curve of the particle size distribution is obtained by using a laser diffraction/scattering particle size distribution analyzer (for example, Microtrack MT3300, manufactured by Nikkiso Co., Ltd.).
  • a medium may appropriately be selected, but for example, methanol or the like may be used.
  • the boron nitride is a pulverized one.
  • the boron nitride is a pulverized one, generation of sparks can be suppressed more.
  • the pulverization can be carried out by a method and condition by which the average particle size and the particle size distribution of the boron nitride can be made to be in the above ranges.
  • the pulverization is carried out by appropriately selecting the kind and the condition of a pulverizer.
  • the pulverizer may be, for example, a jet mill, a hammer mill, a ball mill, a pin mill or the like.
  • the boron nitride may be regulated to the average particle size or the particle size distribution in the above range by being classified.
  • the composition of the present disclosure is not limited, but the content of the boron nitride is preferably 0.1 to 10% by mass, more preferably 0.1 to 2.0% by mass, still more preferably 0.1 to 1.5% by mass and further still more preferably 0.1 to 1.0% by mass.
  • the content of the boron nitride is too low, there arises such a risk that it becomes difficult for a covering material of a foamed electric wire to be obtained to be provided with fine cells; when too high, there arises such a risk that the production cost becomes high.
  • the foam molding composition of the present disclosure may further contain a polyatomic anion-containing inorganic salt in the range of not impairing the advantageous effects of the present disclosure.
  • the polyatomic anion-containing inorganic salt includes one disclosed in U.S. Patent No. 4,764,538 .
  • the foam molding composition of the present disclosure may further contain sulfonic acid, phosphonic acid or salts thereof, zeolite and the like in the range of not impairing the advantageous effects of the present disclosure.
  • an organic foam nucleating agent such as ADCA (azodicarbonamide), DPN (N,N'-dinitropentamethylenetetramine) or OBSH (4,4'-oxybisbenzenesulfonylhydrazide).
  • the foam molding composition of the present disclosure may further contain, other than the resin (A) and the compound (B), conventionally well-known fillers in the range of not impairing the advantageous effects of the present disclosure.
  • the fillers include graphite, carbon fiber, coke, silica, zinc oxide, magnesium oxide, magnesium sulfate, tin oxide, antimony oxide, calcium carbonate, magnesium carbonate, glass, talc, mica, aluminum nitride, calcium phosphate, sericite, diatomaceous earth, silicon nitride, fine silica, fumed silica, alumina, zirconia, quartz powder, kaolin, bentonite and titanium oxide.
  • the shape of the filler is not limited, and includes fibrous, needle, powdery, granular, bead shapes and the like. Here, the fillers are different from the boron nitride.
  • the foam molding composition of the present disclosure may further contain a thermoplastic resin other than the resin (A).
  • a thermoplastic resin other than the resin (A) include general-purpose resins such as polyethylene resins, polypropylene resins, vinyl chloride resins and polystyrene resins; and engineering plastics such as polyamide (PA), polycarbonate, polybutylene terephthalate (PBT) and silicon resins.
  • the foam molding composition may contain a thermosetting elastomer and a thermoplastic elastomer.
  • the foam molding composition of the present disclosure may further contain other components of additives and the like.
  • the other components include fillers such as glass fiber, glass powder and asbestos fiber, and reinforcing agents, stabilizers, lubricants, pigments, flame retarders and other additives.
  • the foam molding composition of the present disclosure can also be obtained, for example, by a production method (hereinafter, referred to as "production method of the composition") including a mixing step of mixing the resin (A) and the compound (B) and as required, a boron nitride, fillers, additives and the like to be added to thereby obtain a mixture.
  • production method of the composition including a mixing step of mixing the resin (A) and the compound (B) and as required, a boron nitride, fillers, additives and the like to be added to thereby obtain a mixture.
  • a method of the mixing can use a conventionally well-known method or the like, but a mixing method in which the compound (B) is hardly aggregated is preferable.
  • the mixing method includes methods using a Henschel mixer, a ribbon mixer, a V blender, a ball mill or the like.
  • the method also includes, for example, a method of mixing by melt kneading.
  • a production method of the foam molding composition of the present disclosure may be a method including a kneading step of kneading the mixture obtained in the above mixing step.
  • kneading pellets can be obtained.
  • the kneading can be carried out, for example, by a method using a conventionally well-known melt kneader such as a single-screw extruder or a twin-screw extruder.
  • thermoplastic resin other than the above-mentioned resin; the boron nitride; the polyatomic anion-containing inorganic salt; the fillers; the other additives; and the like as already described as being capable of being contained in the foam molding composition of the present disclosure can appropriately be added in each step of the production method of the foam molding composition according to the property and the like of the each component.
  • a fluororesin and a boron nitride may further be added.
  • the foam molding composition of the present disclosure can suitably be used as a foaming composition. Further, the foam molding composition can suitably be used as a composition for electric wire covering to form a covering material of an electric wire.
  • a method for producing a foam molded body of the present disclosure comprises a step of foam molding the foam molding composition.
  • the method of foam molding the foam molding composition is not limited, and for example, a conventionally well-known method can be used; examples thereof include a method using a continuous gas injection method in which a gas is used in the resin melted (melted resin) and the foam molding composition of the present disclosure is charged in a screw extruder designed for foaming operation.
  • the gas may be, for example, an inert gas such as chlorodifluoromethane, nitrogen, carbon dioxide, argon, helium or flon, or a mixture thereof; the gas may be introduced as a pressurized gas in the melted resin in the extruder, or may be generated by mixing a chemical foaming agent in the melted resin. The gas is dissolved in the melted resin in the extruder.
  • an inert gas such as chlorodifluoromethane, nitrogen, carbon dioxide, argon, helium or flon, or a mixture thereof
  • the gas may be introduced as a pressurized gas in the melted resin in the extruder, or may be generated by mixing a chemical foaming agent in the melted resin.
  • the gas is dissolved in the melted resin in the extruder.
  • the gas dissolved in the melted resin comes out from the melted material by sudden decline of the pressure of the melted material when the melted material comes out from an extrusion die.
  • the extrudate extruded from the extruder is then cooled and solidified, for example, by a method in which the extrudate is introduced in water.
  • the foam molded body since being obtained by foam molding the foam molding composition, is low in the dielectric constant, presents a stable outer diameter and is low in the weight, and can provide the shape stable in the size including the wire diameter, the thickness and the like as a covering material described later.
  • the total volume of cells in the foam molded body can appropriately be regulated according to applications, for example, by regulation of the amount of the gas to be introduced in the extruder, and the like, or by selection of the kind of the gas to be dissolved.
  • the foam molded body is obtained as a molded body molded according to applications in extrusion from the extruder.
  • the molding method is not limited as long as being thermal melt molding, and examples thereof include extrusion foam molding, injection foam molding and metal mold foam molding.
  • the shape of the foam molded body is not limited, and can be made into various shapes such as a covering material of the foamed electric wire, filament shapes such as a wire rod or the like, sheet, film, rod and pipe shapes.
  • the foam molded body can be used, for example, as an electric insulating material, a heat insulating material, a sound insulating material, a lightweight structural material such as a floating material, a cushioning material such as a cushion, and the like. Further, the foam molded body can especially suitably be used as a covering material of the foamed electric wire.
  • the foam molded body to be obtained contains a melted and solidified body of the foam molding composition of the present disclosure and cells, and it is preferable that the cells are homogeneously distributed in the melted and solidified body.
  • the average cell size of the cells is not limited, but is, for example, preferably 100 ⁇ m or smaller and more preferably 60 ⁇ m or smaller, and is preferably 0.1 ⁇ m or larger.
  • the foaming ratio of the foam molded body is not limited, but is preferably 10% or higher and more preferably 15% or higher.
  • the upper limit of the foaming ratio is not limited, but is, for example, 80%.
  • the surface of the foam molded body of the present disclosure is smoother than that of conventional foam molded bodies is one of features of the foam molded body. Due to that the surface is smooth, the foam molded body can suitably be utilized for foamed members excellent in slidability, and the like.
  • the surface of the foam molded body can be evaluated by scanning the surface by a bare hand and observing the degree of catching (protrusions) transmitted to the hand at this time.
  • the electric wire surface can also be evaluated numerically, as described later, by measuring an electric wire surface by a laser microscope, carrying out correction in a specified electric wire region of obtained image data by using quadratic curved surface correction as surface shape correction, and thereafter calculating the surface roughness of 500 ⁇ 2,000 ⁇ m. It is preferable that the surface roughness is smaller than 10.0 ⁇ m.
  • a method for producing an electric wire of the present disclosure includes a step of covering a core wire with the foam molding composition to thereby obtain the electric wire.
  • the foam molding composition By using the foam molding composition, there can be formed a foamed electric wire equipped with a covering material having fine and uniform cells. It is preferable that the step of obtaining the electric wire involves foam molding the foam molding composition.
  • the electric wire obtained by the production method of the electric wire is composed of the covering material formed from the foam molding composition and the core wire.
  • the electric wire obtained by covering the core wire with the foam molding composition is also one aspect in the present disclosure.
  • the covering material since being obtained by covering the core wire with the foam molding composition, has fine and uniform cells.
  • the covering material is low in the dielectric constant, presents a stable outer diameter and is low in the weight, and can provide the shape stable in the size including the wire diameter, the thickness and the like.
  • the covering material has the smooth surface as in the above foam molded body, and exhibits similar physical properties.
  • the electric wire can be fabricated by a conventionally similar method, except for covering the core wire with the above-mentioned foam molding composition, and can be produced, for example, by using extrusion foam molding.
  • the preferable extrusion condition can appropriately be selected according to the formulation of the composition to be used and the size of the electric wire to be used.
  • Examples of a method of covering the core wire with the foam molding composition include a method in which the foam molding composition of the present disclosure is charged in a screw extruder designed for foaming operation, while a gas soluble to the melted resin is used and a continuous gas injection method is used.
  • the gas may be the same gas as the gas to be used in the production method of the foam molded body.
  • the obtained covering material contains a melted and solidified body of the foam molding composition of the present disclosure and cells, and it is preferable that the cells are distributed homogeneously in the melted and solidified body.
  • the average cell size of the cells is not limited, but is, for example, preferably 200 ⁇ m or smaller, more preferably 100 ⁇ m or smaller, still more preferably 50 ⁇ m or smaller, further still more preferably 40 ⁇ m or smaller, especially preferably 30 ⁇ m or smaller and further especially preferably 20 ⁇ m or smaller.
  • the average cell size is preferably 0.1 ⁇ m or larger, more preferably 0.5 ⁇ m or larger and more preferably 1 ⁇ m or larger.
  • Such a structure of the covering material is obtained due to a combination of the resin (A) and a specific compound (B) in the foam molding composition of the present disclosure.
  • the average cell size is a value determined by taking an image of a covering material cross section by a scanning electron microscope (SEM), calculating the diameter of each cell by image processing and averaging the diameters.
  • SEM scanning electron microscope
  • the foaming ratio of the covering material is preferably 10% or higher, more preferably 20% or higher, still more preferably 30% or higher and further still more preferably 43% or higher.
  • the upper limit is not limited, but is, for example, 90%. Alternatively, the upper limit of the foaming ratio may be 80%. When the foaming ratio becomes high, cell breaking and cell merging occur and a desired molded article becomes unable to be obtained.
  • the foaming ratio is a value determined as ((a specific gravity of a resin - a specific gravity of a foam)/the specific gravity of the resin) ⁇ 100.
  • the foaming ratio can appropriately be regulated according to applications, for example, by regulation of the amount of the gas to be introduced in the extruder, and the like, or by selection of the kind of the gas to be dissolved.
  • the number of sparks per 3,500 m of the covering material is preferably less than 5, more preferably less than 3 and still more preferably less than 1.
  • the number of sparks is a value obtained by measurement at a voltage of 1,500 V by a Beta LaserMike Sparktester HFS1220.
  • a material of the core wire may be, for example, a metal conductor material such as, silver, copper or aluminum.
  • the material may be a single material, or may be a material plated with silver, tin or the like. Alternatively, carbon may be used as a conductor.
  • the core wire is one having a diameter of 0.02 to 3 mm.
  • the diameter of the core wire is more preferably 0.04 mm or larger, still more preferably 0.05 mm or larger and especially preferably 0.1 mm or larger. It is more preferable that the diameter of the core wire is 2 mm or smaller.
  • the core wire may be a solid wire, or may also be a twisted wire in which a plurality of core wires are twisted.
  • the electric wire has a thickness of the covering material of 0.02 to 3.0 mm. It is also preferable that the thickness of the covering material is 2.0 mm or smaller.
  • the conductor may also have a shape such as a round, flat or rectangular shape.
  • the foamed electric wire is composed of the core wire and the covering material covering the core wire.
  • the foamed electric wire can suitably be used as cables which connect computers and their peripheral equipment, cables which communicate high capacities of images and sounds at high speed, cables which connect between servers of data centers, for example, LAN cables, USB cables, lightning cables, HDMI(R) cables and QSFP cables, electric wires for aerospace, underground transmission cables, submarine power cables, high-tension cables, superconducting cables, wrapping electric wires, electric wires for cars, wire harnesses and electrical wiring, electric wires for robots and FA, electric wires for OA equipment, electric wires for information devices (optical fiber cables, LAN cables, HDMI(R) cables, lightning cables, audio cables and the like), internal wiring for communication base stations, large-current internal wiring (inverters, power conditioners, battery systems, and the like), internal wiring for electronic devices, wiring for small electronic devices and mobile devices, wiring for moving parts, internal wiring for electric devices, internal wiring for measurement apparatuses, power cables (for construction, wind/solar
  • the electric wire may also have a two-layer structure (skin-foam) in which a non-foamed layer is inserted between the core wire and the covering material, a two-layer structure (foam-skin) in which a non-foamed layer is coated as an outer layer, or a three-layer structure (skin-foam-skin) in which a non-foamed layer is coated as an outer layer of the skin-foam.
  • the non-foamed layer of the electric wire is not limited, and specifically, may be a resin layer composed of a resin such as polyaryl ether ketone (PAEK) (more specifically, for example, polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ketone (PEK) or polyether ether ketone ketone (PEEKK) and the like), polyphenylene sulfide (PPS), polyether sulfone (PES), liquid crystal polymer (LCP), polysulfone (PSF), amorphous polyarylate (PAR), polyether nitrile (PEN), thermoplastic polyimide (TPI), polyimide (PI), polyether imide (PEI), polyamideimide (PAI), fluororesin or the like.
  • PAEK polyaryl ether ketone
  • PEEK polyaryl ether ketone
  • PEEK polyether ether ketone
  • PES polyether ketone ket
  • a single-screw extruder used for extrusion of a foamed insulating layer had a cylinder diameter of 35 mm, an L/D of 32, a die inner diameter of 0.8 mm and a tip outer diameter of 1.50 to 5.0 mm.
  • the single-screw extruder was operated at a cylinder temperature of 280 to 400°C and at a screw rotation speed of 5 to 30 rpm and a resin composition obtained as described above was fed from a hopper.
  • the melted resin composition discharged formed an insulating layer of 0.3 mm to 0.8 mm in thickness on a conductor (diameter: 0.5 mm, cross-sectional area: 0.20 mm 2 , annealed copper solid wire) to thereby obtain an insulated electric wire.
  • the line speed at this time was set at 20 to 200 m/min.
  • a nitrogen gas was introduced from a central segment C part of the barrel by using a gas injector device and the volume of the nitrogen gas to be introduced was regulated to a target foaming ratio.
  • Molding of a foamed electric wire was carried out by setting pellets (composition) prepared by melt kneading so as the amount to be added be a predetermined value to an extruder temperature being a temperature shown in Table 2, and adjusting the extrusion temperature, the flow volume (pressure) of a nitrogen gas to be introduced, the extrusion speed and the take-over speed.
  • the electric wire extrusion condition is shown in Table 3.
  • the molding was carried out continuously for 1 hour, and for 3,000 m where the molding became and remained stable, fluctuation in the wire diameter and sparking-out were observed. Further, for the obtained foamed electric wire, the foaming ratio and the average cell size were measured, and the surface condition was observed and the surface roughness was measured, by the following methods.
  • Pellets in which 0.5 part by mass of 2,2'-methylenebis(4,6-di-t-butyphenyl) sodium phosphate (crystal nucleating agent, ADK STAB NA-11, melting point: ⁇ 400°C, manufactured by Adeka Corp.) was added to the resin (1) were subjected to foamed electric wire molding at an extruder rotation speed of 15 rpm, at a flow volume of a nitrogen gas introduced of 11 cc/min and at a take-over speed of 105 m/min to thereby obtain a targeted foamed electric wire having an outer diameter of 1.28 mm.
  • the standard deviation of the variation in the wire diameter gave a good value of 0.011, and the number of sparks gave a very good value of 2.
  • the foaming ratio gave a good value of 28% and the average cell size gave a good value of 42 ⁇ m; the surface condition was extremely good to touch and the surface roughness gave a very good value of 9.6 ⁇ m.
  • Pellets in which 1.0 part by mass of 2,2'-methylenebis(4,6-di-t-butyphenyl) sodium phosphate (crystal nucleating agent, ADK STAB NA-11, manufactured by Adeka Corp.) was added to the resin (1) were subjected to foamed electric wire molding at an extruder rotation speed of 15 rpm, at a flow volume of a nitrogen gas introduced of 17 cc/min and at a take-over speed of 100 m/min to thereby obtain a targeted foamed electric wire having an outer diameter of 1.32 mm.
  • the standard deviation of the variation in the wire diameter gave a good value of 0.012, and the number of sparks gave a very good value of 1.
  • the foaming ratio gave a good value of 30% and the average cell size gave a good value of 35 ⁇ m; the surface condition was extremely good to touch and the surface roughness gave a very good value of 9.3 ⁇ m.
  • Pellets in which 1.0 part by mass of 2,2'-methylenebis(4,6-di-t-butyphenyl) sodium phosphate (crystal nucleating agent, ADK STAB NA-11, manufactured by Adeka Corp.) was added to the resin (2) were subjected to foamed electric wire molding at an extruder rotation speed of 15 rpm, at a flow volume of a nitrogen gas introduced of 15 cc/min and at a take-over speed of 98 m/min to thereby obtain a targeted foamed electric wire having an outer diameter of 1.31 mm.
  • the standard deviation of the variation in the wire diameter gave a good value of 0.014, and the number of sparks gave a very good value of 3.
  • the foaming ratio gave a good value of 32% and the average cell size gave a good value of 33 ⁇ m; the surface condition was extremely good to touch and the surface roughness gave a very good value of 8.8 ⁇ m.
  • Pellets in which 1.0 part by mass of 2,2'-methylenebis(4,6-di-t-butyphenyl) sodium phosphate (crystal nucleating agent, ADK STAB NA-11, manufactured by Adeka Corp.) was added to the resin (3) were subjected to foamed electric wire molding at an extruder rotation speed of 15 rpm, at a flow volume of a nitrogen gas introduced of 14 cc/min and at a take-over speed of 97 m/min to thereby obtain a targeted foamed electric wire having an outer diameter of 1.35 mm.
  • the standard deviation of the variation in the wire diameter gave a good value of 0.015, and the number of sparks gave a very good value of 3.
  • the foaming ratio gave a good value of 35% and the average cell size gave a good value of 36 ⁇ m; the surface condition was extremely good to touch and the surface roughness gave a very good value of 9.5 ⁇ m.
  • the standard deviation of the variation in the wire diameter gave a good value of 0.017, and the number of sparks gave a very good value of 3.
  • the foaming ratio gave a good value of 25% and the average cell size gave a good value of 44 ⁇ m; the surface condition was extremely good to touch and the surface roughness gave a very good value of 10.1 ⁇ m.
  • the standard deviation of the variation in the wire diameter gave a good value of 0.011, and the number of sparks gave a very good value of 2.
  • the foaming ratio gave a good value of 30% and the average cell size gave a good value of 37 ⁇ m; the surface condition was extremely good to touch and the surface roughness gave a very good value of 9.3 ⁇ m.
  • Pellets in which nothing was added to the resin (1) were subjected to foamed electric wire molding at an extruder rotation speed of 15 rpm, at a flow volume of a nitrogen gas introduced of 10 cc/min and at a take-over speed of 70 m/min. Almost no foaming was observed; the outer diameter scattered; and the variation in the electrostatic capacity was very large. No targeted foamed electric wire could be obtained.
  • Pellets in which 1.0 part by mass of an alumina was added to the resin (3) were subjected to foamed electric wire molding at an extruder rotation speed of 15 rpm, at a flow volume of a nitrogen gas introduced of 12 cc/min and at a take-over speed of 92 m/min to thereby obtain a foamed electric wire having an outer diameter of 1.29 mm.
  • the standard deviation of the variation in the wire diameter gave an unstable value of 0.102, and the number of sparks gave a very bad value of 100 or more.
  • the foaming ratio gave a value of 30% and the average cell size gave a large value of 82 ⁇ m; the surface condition was poor and the surface roughness gave a bad value of 16.4 ⁇ m.
  • the pyrolysis temperature of a resin was defined as a 1%-weight loss temperature when the resin was heated in air at 10°C/min by TG (weight change measurement by heating).
  • the measurement was carried out by using a differential thermogravimetric simultaneous measuring apparatus. TG/DTA6300, manufactured by Seiko Instruments Inc.
  • the melting point of a resin was defined as a temperature corresponding to a peak when the measurement was carried out at a temperature-increasing rate of 10°C/min by using an RDC220 (manufactured by Seiko Instruments Inc.).
  • the melting point of a resin was determined as a temperature corresponding to the local maximum value in a heat-of fusion curve when the temperature was increased at a rate of 10°C/min by using a differential scanning calorimetry (DSC) device.
  • DSC differential scanning calorimetry
  • the glass transition temperature was measured according to JIS K7121 by using a differential scanning calorimetry (DSC) device under the measurement condition of a temperature-increasing rate of 20°C/min.
  • DSC differential scanning calorimetry
  • the MFR of a resin was measured according to ASTM D1238 by using a KAYENESS Melt Indexer Series 4000 (manufactured by Yasuda Seiki Seisakusho, Ltd.) and by using a die of 2.1 mm in diameter and 8 mm in length.
  • the MFR was defined as a value by the measurement at 380°C and at a load of 5 kg; and in the case of a PPS resin, the MFR was defined as a value by the measurement at 315°C and at a load of 5 kg.
  • the outer diameter of an electric wire was measured by using a LASER MICRO DIAMETER LDM-303H-XY (manufactured by Takikawa Engineering Co., Ltd.).
  • the number of sparks per 3,500 m was measured by using a Beta LaserMike Sparktester HFS1220 at a voltage of 1,500 V.
  • the foaming ratio was determined as a specific gravity of a resin ⁇ a specific gravity of foam / the specific gravity of the resin ⁇ 100 .
  • the average cell size was determined by taking a SEM image of an electric wire cross section, calculating the diameter of each cell by image processing, and averaging the diameters.
  • the surface condition was evaluated by scanning the surface of a covered electric wire by a bare hand and evaluating the degree of catching (protrusions) transmitted to the hand at this time.
  • the electric wire surface was measured by a laser microscope, manufactured by Keyence Corp.; there was carried out correction in a specified electric wire region of obtained image data by using quadratic curved surface correction as surface shape correction; and thereafter, the surface roughness of 500 ⁇ 2,000 ⁇ m was calculated.
  • Example 1 Example 2 Exampl e3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Resin A Resin 1 Resin 1 Resin 2 Resin 3 Resin 4 Resin 1/ Resin 2 Resin 1 Resin 3 Compound B NA-11 NA-11 NA-11 NA-11 NA-11 none alumina Amount added parts by mass 0.5 1.0 1.0 1.0 1.0 none 1.0 Rotation Speed of Extruder rpm 15 15 15 15 20 15 15 15 15 Take-over speed m/min. 105 100 98 97 110 102 70 92 Volume of gas introduced cc/min.
  • the foam molding composition of the present disclosure is suitable, in particular, as a material for forming a covering material of a foamed electric wire.

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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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  • Processes Specially Adapted For Manufacturing Cables (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
EP21852439.5A 2020-08-03 2021-07-27 COMPOSITION FOR FOAM MOLDING, EXPANDED MOLDED BODY, ELECTRIC WIRE, METHOD FOR MANUFACTURING EXPANDED MOLDED BODY, AND METHOD FOR MANUFACTURING ELECTRIC WIRE Pending EP4190853A4 (en)

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PCT/JP2021/027647 WO2022030293A1 (ja) 2020-08-03 2021-07-27 発泡成形用組成物、発泡成形体、電線、発泡成形体の製造方法、及び、電線の製造方法

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US4764538A (en) 1987-12-16 1988-08-16 E. I. Du Pont De Nemours And Company Foam nucleation system for fluoropolymers
JPH11130892A (ja) 1997-10-31 1999-05-18 Asahi Denka Kogyo Kk 壁紙用組成物
US7241826B2 (en) * 2001-06-26 2007-07-10 Daikin Industries, Ltd. Resin composition, process for production thereof, and foam-insulated electric wire
US20060134416A1 (en) * 2004-12-17 2006-06-22 Hiroshi Kubo Flame retardant electrical wire
CN102812524B (zh) 2010-03-25 2015-05-27 古河电气工业株式会社 发泡电线及其制造方法
JP2013147566A (ja) 2012-01-19 2013-08-01 Mitsui Chemicals Inc 発泡核剤、発泡体用組成物、発泡体及びその製造方法
JP6424681B2 (ja) * 2015-03-05 2018-11-21 日立金属株式会社 発泡樹脂成形用ペレットの製造方法
JP6740642B2 (ja) 2016-03-03 2020-08-19 日立金属株式会社 絶縁電線の製造方法
US11104775B2 (en) * 2016-04-29 2021-08-31 Imerys Talc America, Inc. Controlled polymer foaming using a hybrid nucleating agent formed from a mineral and an organic nucleating agent
MX2020005632A (es) * 2017-12-01 2020-09-03 Cable Components Group Llc Composiciones espumables y metodos para fabricar articulos espumosos.
CN110591331A (zh) * 2019-08-16 2019-12-20 杭州博适特新材料科技有限公司 一种改性聚苯硫醚或改性聚苯醚发泡珠粒及其制备方法

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